Hydroxylated polymers useful as additives for fuels and lubricants

ABSTRACT

Hydroxylated polymeric additives useful as additives, for example as dispersants for lubricants and hydrocarbon fuels, and multi-functional dispersant-viscosity index improvers for lubricants, can be prepared by the reaction of metal salts of polyols with a halogen containing olefin polymer, particularly ethylene containing polymers, such as: the halogenated terpolymer of ethylene, a C 3  to C 18  straight or branched chain α-olefin and a C 5  to C 14  acyclic or alicyclic nonconjugated diolefin; a terpolymer of ethylene, a C 3  to C 18  alpha olefin and a C 5  to C 14  halogen-containing olefin; halogenated copolymers of ethylene and a C 3  to C 18  straight or branched chain α-olefin; etc.

This is a division, of application Ser. No. 402,609, filed Oct. 1, 1973.

BACKGROUND OF THE INVENTION Field Of The Invention

This invention relates to oil soluble hydroxylated olefin polymers,e.g., the hydroxylated reaction products of halogen containing polymerswill polyol metal salts, a method for their preparation, and tocompositions comprising a major proportion of a fuel or lubricant and aminor proportion of said hydroxylated polymer as a sludge dispersantand/or V.I. improver. More preferably this invention relates tocopolymers of ethylene and higher α-olefins and to terpolymerscomprising ethylene, a higher α-olefin and a nonconjugated diolefin,which have been halogenated or hydrohalogenated, and then hydroxylatedby reaction with a metal salt of a polyol. Alternatively, in thesynthesis of the terpolymer, the nonconjugated diene may be replaced inwhole or in part by an acyclic or alicyclic halo-olefin to therebydirectly give the halogen containing polymer which is then reacted withsaid metal salt.

2. Prior Art

Compositions comprising polymeric or high molecular weight materialswhich incorporate hydroxyl groups have been described in U.S. andforeign patents as dispersants and/or viscosity index improvers forfuels and/or lubricants. For example:

U.S. Pat. No. 3,621,004 discloses lubricant additives containinghydroxylated polymers formed by copolymerizing ethylene, alkyl (C₈ -C₂₀)methacrylates, and β-hydroxyethyl methacrylate as viscosity indeximprovers and sludge dispersants.

U.S. Pat. No. 3,687,849; German Pat. No. 1,929,811; and Canadian Pat.728,709, disclose lubricant compositions containing hydroperoxidizedolefin copolymers with grafted hydroxy monomers such as allyl alcohol,β-hydroxyethyl methacrylate, and vinyl acetate (hydrolyzed subsequentlyto vinyl alcohol groups) which act as ash free sludge dispersants.

U.S. Pat. No. 3,642,633 discloses lubricant compositions containingterpolymers of vinyl toluene, a mixture of lauryl and stearylmethacrylate, and β-hydroxyethyl methacrylate; or terpolymers containingmethacrylic acid ethoxylated to β-hydroxyethyl methacrylate; whichterpolymers are pour depressants, viscosity index improvers, and sludgedispersants.

U.S. Pat. No. 3,888,067 discloses lubricant additives containinghydroxylated ethylene-propylene rubbers made by reduction ofhydroperoxidized (by a hydroperoxide) polymer.

U.S. Pat. No. 3,381,022 discloses lubricant additives made by thereaction of alkenyl succinic anhydride and polyalcohols as sludgedispersants.

Summary Of The Invention

It has now been found that highly effective dispersants, andmultifunctional dispersant-viscosity index improvers, for fuels andlubricants, are the reaction products of halogen containing ethyleneα-olefin copolymers, e.g., a halogenated or hydrohalogenated copolymerof ethylene and a C₃ -C₁₈ alpha olefin, or terpolymer of ethylene, a C₃to C₁₈ straight or branched chain α-olefin and a C₅ to C₁₄ acyclic oralicyclic nonconjugated diolefin, with the metal salt of a polyol.

The halogen in the halogenated or hydrohalogenated polymer is either onthe backbone carbon atoms, or can be external to the backbone chain ofcarbon atoms. The halogen can be incorporated into the polymer byhalogen replacement of a hydrogen, or in the terpolymer, by: addition ofhalogen halide to an olefinic double bond in a hydrocarbon moiety whichis pendant to the backbone chain of carbon atoms, or by allylichalogenation of a similarly located olefinic double bond. Alternatively,the halogen can be incorporated directly in a terpolymer by using a C₅to C₁₄ halogen-containing olefin in place of part or all of theabove-noted diolefin.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The Polymer

Copolymers of ethylene and higher C₃ -C₁₈ α-olefins, which can behalogenated for use in the invention, will generally comprise about30-85 mole % ethylene and 70-15 mole % higher α-olefin. Ethylene-C₃ toC₁₈ α-olefin-C₅ to C₁₄ nonconjugated diolefin terpolymers, which are tobe halogenated or hydrohalogenated will generally comprise about 30 to84.5 mole % ethylene; about 15 to 69.5 mole % of the higher C₃ to C₁₈olefin, and about 0.5 to 20 mole % of the diolefin. Preferred arepolymers of 40 to 70 mole % ethylene, 20 to 58 mole % of the higherolefin and 2 to 10 mole % of diolefin. On a weight basis usually atleast 2 or 3 wt. % of the terpolymer will be the diolefin. Mixtures ofmonoolefins and/or mixtures of diolefins can be used.

Alternatively, a C₅ to C₁₄ halogen-containing monomer can be directlyincorporated in the terpolymer during synthesis by substituting the C₅to C₁₄ halogen-containing monomer for any part or all of the C₅ to C₁₄diolefin in the above-mentioned terpolymer compositions.

Examples of the above-noted higher C₃ -C₁₈ alpha monoolefins includepropylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-decene,1-dodecene, 1-heptadecene, etc. Preferred are the C₃ -C₈ monoolefins,particularly propylene.

Representative non-limiting examples of the nonconjugated diolefinsinclude:

A. straight chain acyclic dienes such as: 1,4-hexadiene, 1,5-heptadiene,1,6-octadiene.

B. branched chain acyclic dienes such as: 5-methyl-1, 4-hexadiene;3,7-dimethyl 1,6-octadiene; 3,7-dimethyl 1,7-octadiene; and the mixedisomers of dihydromyrcene and dihydroocimene.

C. single ring alicyclic dienes such as: 1,4-cyclohexadiene;1,5-cyclo-octadiene; 1,5-cyclododecadiene; 4-vinyl-cyclohexene; 1-allyl4-isopropylidene cyclohexane; 3-allyl-cyclopentene; 4-allyl cyclohexeneand 1-isopropenyl 4(4-butenyl) cyclohexane.

D. multi-single ring alicyclic dienes such as: 4,4'-dicyclopentenyl and4,4'-dicyclohexenyl dienes.

E. multi-ring alicyclic fused and bridged ring dienes such as:tetrahydroindene; methyl tetrahydroindene; dicyclopentadiene;bicyclo(2,2,1) hepta 2,5-diene; alkenyl, alkylidene, cycloalkenyl andcycloalkylidene norbornenes such as: 5-methylene-2-norbornene;5-ethylidene-2-norbornene; 5-methylene-6-methyl-2-norbornene;5-methylene-6,6-dimethyl-2-norbornene; 5-propenyl-2-norbornene;5-(3-cyclopentenyl)-2-norbornene and 5-cyclohexylidene-2-norbornene.

A variety of acyclic or alicyclic halo-olefins having 1 or 2 halogensmay be employed as monomers, provided the halogen in the compound issufficiently stable so as not to be removed or interfere with thepolymerization. Suitable nonlimiting examples of halo-olefins include:5-chlorohexene-1; 3-(1-chloroethyl) pentene-1; 4-(1-chloroethyl)hexene-1; 5-chloromethyl norbornene-2 and 3-chloro,3,4-dihydrodicyclopentadiene etc., 5-chloro methyl or 5-bromomethylnorbornene-2 which is readily prepared from allyl chloride or allylbromide and cyclopentadiene or dicyclopentadiene by a Diels-Aldersynthesis is particularly preferred.

In general, the preparation of copolymers of terpolymers suitable forthe practice of this invention by means of Ziegler-Natta catalysts isknown in the prior art, for example see U.S. Pat. Nos. 2,933,480;3,000,866; and 3,093,621. These polymers which are primarily producedfor use in elastomeric compositions, are usually characterized by thesubstantial absence of chain or backbone unsaturation, and when madefrom non-conjugated dienes contain sites of unsaturation in groups whichare pendant to or are in cyclic structures outside the main polymerchain. Ethylene-propylene copolymers andethylene-propylene-non-conjugated diolefin terpolymers are knownarticles of commerce. In fact, various examples of such commerciallyavailable copolymers or terpolymers are VISTALON, an elastomericcopolymer of ethylene and propylene, or terpolymer of ethylene,propylene and 5-ethylidene, 2-norbornene, marketed by Exxon ChemicalCo., New York, N.Y., and NORDEL, a terpolymer of ethylene, propylene and1,4-hexadiene, marketed by E.I. duPont De Nemours & Co., Wilmington,Del.

In general, the catalyst compositions used to prepare these polymerscomprise a principal catalyst consisting of a transition metal compoundfrom Groups IVb, Vb and VIb of the Periodic Table of the Elements,particularly compounds of titanium and vanadium, and organometallicreducing compounds from Groups IIa, IIb and IIIa, particularlyorganoaluminum compounds which are designated as cocatalysts. Preferredprincipal catalysts of vanadium have the general formula VO_(z) X_(t)wherein z has a value of zero or 1 and t has a value of 2 to 4. X isindependently selected from the group consisting of halogens having anatomic number equal to or greater than 17, acetylacetonates,haloacetylacetonates, alkoxides and haloalkoxides. Non-limiting examplesare: VOCl₃ ; VO(AcAc)₂ ; VCCl₂ (OBu); V(AcAc)₃ ; and VOCl₂ (AcAc) whereBu is n-butyl or isobutyl and (AcAc) is an acetylacetonate.

Preferred cocatalysts have the general formula AlR'_(m) X'_(n) whereinR' is a monovalent hydrocarbon radical selected from the groupconsisting of C₁ to C₁₂ alkyl, alkylaryl, arylalkyl and cycloalkylradicals, X' is a halogen having an atomic number equal to or greaterthan 17, m is a number from 1 to 3 and the sum of m and n is equal to 3.Non-limiting examples of useful cocatalysts are: Al(Et)₃ ; Al(IsoBu)₃ ;Et₂ AlCl; EtAlCl₂ and Et₃ Al₂ Cl₃.

Synthesis of the polymers, which may be conducted in batch, staged orcontinuous reactors, are preferably run in the presence of a purifiedsolvent such as hexane which has been percolated thru LINDE 3A catalystand in the absence of moisture, air or oxygen and catalyst poisons. Anatmosphere of oxygen-free nitrogen is preferably maintained above thereactants. Monomers, principal catalyst and cocatalyst are fed to thereactor supplied with means for withdrawing the heat of reaction andmaintained under controlled agitation for a time, temperature andpressure sufficient to complete the reaction.

Suitable times of reaction will generally be in the range from 1 to 300minutes, temperatures will usually be in the range of 0° to 100° C. andpressures from atmospheric to 160 psig are generally used. Monomer feedto the reactor per 100 parts by weight of solvent may be in the rangeof: ethylene, 2 to 20 parts by weight; C₃ to C₁₈ α-olefin, 4 to 20 partsby weight; and nonconjugated diene or halo-olefin, when used 0.1 to 10parts by weight.

Principal catalyst, VOCl₃ for example, prediluted with solvents is fedto the reactor so as to provide a concentration in the range of 0.1 to5.0 millimoles per liter. Cocatalyst, for example Et₃ Al₂ Cl₃ is at thesame time fed to the reactor in an amount equal to from 2.0 to 20.0moles of cocatalyst per mole of principal catalyst.

The polymers may have molecular weights M_(n) of about 1000 to 500,000;preferably 10,000 to 200,000; and usually about 20,000 to 100,000. Ingeneral, polymers having a narrow range of molecular weight, asdetermined by the ratio of weight average molecular weight (M_(w)) tonumber average molecular weight (M_(n)) are preferred. Polymers having aM_(w) /M_(n) of less than 10, preferably less than 7, and mostpreferably 4 or less are most desirable. Polymers in this range may beobtained by a choice of synthesis conditions such as choice of principalcatalyst and cocatalyst combination and addition of hydrogen during thesynthesis. Post synthesis treatment such as extrusion at elevatedtemperature and under high shear through small orifices, and fractionalprecipitation from solution may also be used to obtain narrow ranges ofdesired molecular weights. For a comprehensive review of the art see:"Polymer Chemistry of Synthetic Elastomers", edited by Kennedy andTornqvist, Interscience, N.Y. 1969.

While these polymers are essentially amorphous in character bysuperficial inspection, they may contain up to 25 percent by weight ofcrystalline segments as determined by X-ray or differential scanningcalorimetry. Details of these methods for measurement of crystallinityare found in J. Polymer Sci. A-2, 9, 127 (1971) by G. VerStrate and Z.W. Wilchinsky.

Structurally, the polymers suitable for conversion to halides,dihalides, hydrohalides or allylic halides for the practice of thisinvention may be illustrated as copolymers or terpolymers in which thefollowing monomer moieties are linked in the polymer chain in a randomsequence and in a varying number, as typified by the followingstructures: ##STR1## Wherein R is a C₁ to C₁₆ straight or branched chainalkyl radical, R' and R" are independently selected from the groupconsisting of hydrogen and C₁ to C₆ alkyl radicals, and x, y and z arecardinal numbers, typically in the range of 1 to 100. It will beunderstood that the numerical values assigned to x, y and z are notnecessarily totals for any monomer in the polymer but that thesenumerical values express the number of times a given monomer may berepeated in the polymer chain before another monomer is interposed inthe chain.

Halogenated terpolymers may also be produced by direct synthesis, usinga halo-olefin as third monomer, replacing the aforesaid non-conjugateddiene in whole or in part. An illustration of such a terpolymer follows:##STR2## wherein R is a C₁ to C₁₆ alkyl radical; x, y and z are cardinalnumbers in the range of 1 to about 100; and X is Cl or Br.

Halogenation of The Polymers

The halogenation of the polymers can be carried out by dissolving thepolymers in an inert solvent and adding gaseous chlorine or bromine, orliquid bromine, etc. at 0° to 120° C. More specifically, thehalogenation, or hydrohalogenation can be carried out by simplydissolving the polymer in a solvent, preferably a solvent substantiallyinert to the halogen material, and adding halogen, e.g., gaseouschloride, liquid bromine, or a hydrohalogen, e.g., HCl or HBr gas, intothe solution, preferably at rather low temperatures, e.g., 0° to 120° C.Primarily depending on the amount of halogen added and the number ofdouble bonds available, 0.1 to 7.0, e.g., 0.3 to 4.0 wt. % halogen,e.g., Cl or Br, based on the weight of halogen containing polymer, canbe added to the polymer. Hydrogen is replaced by halogen in copolymerhalogenation. In the halogenation of terpolymer, the bromine tends toreact by addition, while the chlorine tends to be incorporated byallylic reaction. If the reaction is carried out in an inert volatilesolvent, then a non-volatile oil can be later added to the reactionproduct solution and the volatile solvent evaporated to thereby form anoil concentrate of the halogen containing polymer for further handling.Alternatively, isolation of the halogenation polymer may be readilycarried out, e.g., by precipitation in media such as acetone orisopropanol or by stripping with steam, etc.

In general, these techniques are known in the art; for examplebromination of terpolymers of ethylene, a C₃ to C₈ α-olefin and a C₅ toC₁₄ non-conjugated diolefin is illustrated in U.S. Pat. No. 3,524,826.

Non-limiting examples of halogenated, hydrohalogenated and allylicallyhalogenated polymers of the invention may be illustrated structurallyas: ##STR3## wherein R is a C₁ to C₁₆, preferably C₁ to C₆, straight orbranched chain alkyl radical; R' and R" are independently selected fromthe group consisting of hydrogen and C₁ to C₆ aliphatic hydrocarbonradicals; x, y and z are cardinal numbers in the range of 1 to about100; X, Y and Y' are independently selected from the group consisting ofhydrogen, chlorine and bromine; A is a carbon to carbon single bond whenY and Y' are hydrogen and n is equal to 1. When A is a carbon to carbondouble bond and n is 0, then Y can be chlorine or bromine and Y' can behydrogen, or Y' can be chlorine or bromine and Y and can be hydrogen.

Polyol Metal Salt

Formation of the metal salt of the polyol, i.e., the alcoholate, can beaccomplished by adding the pure metal, e.g., sodium, in small pieces tothe polyol in a polar solvent. This is well known to the art. Thereaction is carried out under dry nitrogen and the polyol and solventshould also be dry. The reaction proceeds by liberating hydrogen andforming the alcoholate as shown below: ##STR4## Preferably, just enoughmetal is used to metallate one hydroxyl group of a polyol in most cases.

Alcoholates can also be prepared by disproportionation reactions asfollows:

    R'OM + ROH ⃡ ROM + R'OH

if one of the resulting alcohols can be removed.

In general, useful metal salts of alcohols include salts of polyols,i.e., polyhydric alcohols, having in the range of 2 to 12, preferably 2to 6, and most preferably 3 to 6, hydroxyl groups and in the range of 2to 200, preferably 2 to 24 carbon atoms per molecule.

Preferred polyol for making the salts are aliphatic saturated polyolsand include those of the general formulae: ##STR5## wherein R can beindependently selected from the group consisting of hydrogen, C₁ to C₂₀straight or branched chain alkyl radicals, methylol, hydroxy alkylradical, pentaerythritol radical, or other polar substituents such asamine, chlorine, nitro, nitrile, etc. R' can be a C₂ to C₂₀ straight orbranched chain, or alicyclic alkyl radical. R" is usually a C₂ or C₃alkylene group, but can be C₄ and higher alkylene groups; x and y canvary from 1 to 50.

Non-limiting examples of polyols include: ethylene glycol; propyleneglycol (1,2 or 1,3); (1,4) butylene glycol; cyclohexene glycol;glycerine, mannitol; sorbitol, dextrose; sucrose; other sugars;diethylene glycol; dipropylene glycol; polyethylene and polypropyleneglycols; pentaerythritol; di or poly pentaerythritols; trimethylolmethane, ethane, or propane; trimethylol nitro, chloro, nitrilo, oramino methane; neoalkyl glycols, etc. Pentaerythritol is most preferred.

Metal components of the alcohol salts are those metals that formalcoholates. Preferred are alkali metals such as sodium, potassium andlithium; and alkaline earth metals such as magnesium, calcium, strontiumand barium. Most preferred are the alkali metals, particularly sodium.

Halogen Containing Polymer - Metal Salt Reaction

Reaction of the halo-polymer, usually dissolved in a solvent or diluentoil, with the metal salt component will generally be carried out at atemperature in the range of 100° to 210° C., for about 1 to 100 hours,at atmospheric pressure. The metal salt is kept dry until used andexposed to moisture as little as possible in the transfer to thereactor. It is desirable to maintain an inert atmosphere such asnitrogen in the reaction mixture. Any solid reaction products formed canbe later removed by centrifuging or filtration at the end of thereaction. By carrying out the reaction in the presence of an oil, an oilconcentrate of the hydroxylated product will be formed which can then beused directly as an additive. Of course, if desired, the hydroxylatedproduct per se can be recovered by carrying the reaction out in avolatile solvent, which is later evaporated. About 10 to 100%, e.g., 30to 90 mole % of the halogens available may be replaced by hydroxylatedgroups to give a final product with 0.1 to 15.0 wt. %, preferably 0.2 to10 wt. % oxygen based on the hydroxylated polymer per se. Frequently thehydoxylated polymer may also contain 0 to 3 wt. % of halogen remainingafter reaction. Any remaining halogen would contribute mild e.p.properties.

The Compositions

The hydroxylated oil soluble reaction products of this invention can beincorporated in lubricating oil compositions, e.g., automotive crankcaselubricating oils, in concentrations within the range of about 0.01 to 10weight percent, e.g., 0.1 to 7 weight percent, preferably 0.3 to 3.0weight percent, of the total composition. The lubricants to which thehydroxylated products of this invention can be added include not onlyhydrocarbon oils derived from petroleum but also include synthetic oilssuch as alkyl esters of dicarboxylic acids; complex esters ofdicarboxylic acids, polyglycols and alcohols; organic esters ofphosphoric acids, polysilicone oil, etc.

When the products of this invention are used as dispersants in fuelssuch as gasoline, kerosene, diesel fuels, No. 2 fuel oil and middledistillates, a concentration of the additive in the fuel in the range of0.001 to 0.5, preferably about 0.001 to 0.1 weight percent, based on theweight of the total composition, will usually be employed.

The additive may be conveniently dispensed as a concentrate comprising aminor proportion of the additive, e.g., 10 to 45 parts by weight,dissolved in a major proportion of a mineral lubricating oil, e.g., 90to 45 parts by weight, with or without other additives being present.

In the above compositions or concentrates, other conventional additivesmay also be present, including dyes, pour point depressants, antiwearagents such as tricresyl phosphate or zinc dialkyl dithiophosphates of 3to 8 carbon atoms, antioxidants such as N-phenyl α-naphthylamine, tert.octyl phenol sulfide, 4,4'-methylene bis(2,6-di tertbutyl phenol),viscosity index improvers such as ethylenepropylene copolymers,polymethacrylates, polyisobutylene, alkyl fumarate-vinyl acetatecopolymers and the like, as well as other ashless dispersants,detergents and viscosity index improvers, etc.

This invention will be further understood by reference to the followingexamples, which include preferred embodiments of the invention.

Halogenation of Polymers

The following oil soluble random terpolymers, all of which weresubstantially amorphous, were halogenated.

Polymer A was a terpolymer of about 49 wt. % ethylene, 9.7 wt. %5-ethylidene norbornene-2 and the remainder propylene. It had a M_(n)(number average molecular weight) of about 65,000 and a M_(w) /M_(n)ratio of about 3 to 3.5.

Polymer B comprised about 50 wt. % of ethylene, 3.8 wt. % of5-ethylidene norbornene-2 and the remainder propylene. It had a M_(n) ofabout 50,000 and a M_(w) /M_(n) ratio less than 4.

Polymer C comprised about 53 wt. % of ethylene, 3.5 wt. % of1,4-hexadiene and the remainder propylene. It had an estimated M_(n)molecular weight of approximately 50,000.

Polymer D comprised 53 wt. % of ethylene, 7.5 wt. % of 5-ethylidenenorbornene-2 and the remainder propylene. This polymer had a numberaverage molecular weight of about 7500.

Polymer E comprised 46 wt. % of ethylene and 54 wt. % of propylene. Thepolymer had a number average molecular weight of about 55,000.

EXAMPLE 1

In a flask, 560 gms. of Polymer A was dissolved in 7440 gms. of heptaneby stirring at room temperature to make a 7 wt. % solution of Polymer Ain heptane.

A reaction flask was then charged with 2680 gms. of said 7 wt. %solution and heated to 60° C. with stirring. Ten gms. of chlorine (asdetermined by noting the change in weight of the chlorine cylinder usedto supply the chlorine) was bubbled into the solution over a period ofan hour while stirring. Nitrogen was then bubbled through the flaskovernight to evaporate the heptane. 2680 gms. of Solvent 150 Neutral(neutral lubricating oil of 150 SUS. viscosity at 100° F.) was added andheated at 100° C. for 24 hours to give an oil solution. A sample wasfreed from the oil by dialysis through a rubber membrane and contained2.27 wt. % chlorine.

EXAMPLE 2

560 gms. of Polymer B was dissolved in 7400 gms. of heptane in a 12liter flask equipped with a heating mantle, mechanical stirrer, inletfor chlorine, a sodium hydroxide scrubber consisting of 20 gms. of a 50wt. % solution of sodium hydroxide dissolved in water, and athermometer. The composition was stirred at room temperature, e.g.,about 77° F. and allowed to mix over a two-day weekend. The heat wasturned on and the temperature rose to about 80° C. About 1750 ml. ofmaterial was removed from the flask as the flask was too full. The heatwas then maintained in the range of about 75° to 85° C. and chlorineaddition was begun. A total of 12.2 gms. of chlorine was added over aperiod of time of about 40 minutes. Following this, a slow nitrogensparge was carried out overnight at about 90° C. The following day, thedissolved chlorinated composition was removed from the reaction flask. Aportion of the composition was then stripped from heptane by blowingwith nitrogen on a steam bath. Analysis of the chlorinated polymerresidue indicated 1.35 wt. % chlorine content.

EXAMPLE 3

780 gms. of Polymer C was dissolved in a mixture of 5000 gms. of heptaneand 5360 gms. of hexane by stirring at room temperature for 48 hours.3316 gms. of the resulting polymer cement was placed in a 5 liter flaskequipped with a thermometer, condenser, nitrogen sparge, chlorine inletand a stirrer. The flask was then heated to a temperature in the rangeof about 50° to 55° C. and 14.5 gms. of chlorine was added over a 30minute period. The resulting solution was a bright yellow. Followingthis, the solution was sparged with nitrogen for about 12 hours whilemaintaining the temperature at 40° C. Heat was applied and the solventwas evaporated from the mixture at a temperature ranging from 60° to120° C. As the solvent was coming off during evaporation, 3060 gms. of alow pour point Solvent 150 Neutral mineral oil of about 150 SUSviscosity at 100° F., was added. The evaporation and the periodicaddition of the Solvent 150 Neutral was carried out over a total ofabout 16 hours during which time the temperature climbed to a finalpoint of 150° C. Some darkening occurred during the last 3 or 4 hourswhile the temperature was in the general range of about 120° to about150° C. Analysis indicated that the chlorinated polymer contained about2.44 wt. % chlorine.

EXAMPLE 4

To a 10 gal. reactor there was added 1283 gms. of Polymer B along with17,050 gms. of hexane. This mixture was heated with stirring to about50° C. for 24 hours followed by stirring for an additional 48 hours atabout 23° C. The polymer dissolved to form a polymer cement of about 7wt. % polymer.

A first batch of 7400 gms. of the polymer cement was chlorinated with8.4 gms. of chlorine at 60° C. over a period of about 1/2 hour.Following this, the hexane was stripped off by bubbling nitrogen throughwhile simultaneously Solvent 150 Neutral low cold test oil was added. Ittook about 3 to 4 hours at temperatures in the range of 70° to 120° C.to strip off the hexane and to add the oil. Following this, the mixturewas then nitrogen sparged at 80°C. overnight. A second batch of 7400gms. of polymer cement was similarly treated except that 5.2 gms. ofchlorine was added at 65° C. Two batches were combined. A sample of theoil solution was dialized to remove the oil, and the chlorinated polymerper se analyzed for chlorine. It had 0.82 wt. % chlorine.

EXAMPLE 5

10,000 ml. of a 7 wt. % solution of Polymer B in hexane was placed in a12 liter flask heated to 60° C., and 25.2 gms. bromine dissolved in 100ml. of hexane was added to the batch over a period of 1 hour, withstirring. The mixture was nitrogen sparged at 60° C. for 1 hour. Solventwas evaporated from the flask by the nitrogen sparging while heating,while Solvent 150 Neutral oil was periodically added to keep the levelof the liquid even in the flask. The solvent was continuously removeduntil the temperature climbed to 120° C. The resulting oil solution wasa clear dark brown with a slight trace of haze. The brominated polymerper se contained 4.3 wt. % based on the polymer.

EXAMPLE 6

672 gms. of Polymer B was dissolved in 8928 gms. of Solvent 100 Neutralmineral lubricating oil (100 SUS at 100° F.) in a 12 liter flaskequipped with a mechanical stirrer, inlet for Cl, a sodium hydroxidescrubber and a thermometer. A total of 15 gms. of chlorine was addedover a period of about 1 hour and 15 minutes while stirring andmaintaining the temperature in the range of about 60° -64° C. Thecomposition was then sparged with nitrogen overnight and the followingday additional chlorine amounting to another 12.5 gms. was added over aperiod of 45 minutes while maintaining the temperature at 60° C. Theresulting composition was then blown with nitrogen sparging over aweekend. The polymer contained 0.77 wt. % chlorine.

EXAMPLE 7

10,000 ml. of a 7 wt. % solution of Polymer B in hexane was placed in a12 liter flask and a total of 7.2 gms. of bromine was added at 30° C. inthe same manner as described with regard to Example 5 and worked up inthe same manner. The brominated polymer contained 1.54% bromine.

EXAMPLE 8

710 gms. of Polymer D was dissolved in 1633 gms. of hexane whilestirring overnight with warming. The material was then added to a 5liter flask and excess hexane added. 32.3 gms. of chlorine was addedover a period of about 11/2 hours at 50° C. followed by nitrogensparging at 1 hour at 50° C. Following this, 800 gms. of Solvent 100Neutral oil was added with heating and sparging while the hexane wastaken overhead. Finally another 830 gms. of Solvent 100 Neutral oil wasadded with heating and sparging while the hexane was taken overhead; thesparging continued at room temperature overnight. The following morningthe solution was heated at 120° C. with vigorous nitrogen sparge for anadditional hour. The theoretical chlorine content was 2.4 wt. %chlorine.

EXAMPLE 9

279 gms. of a solution, previously formed by dissolving 1750 gms. ofPolymer B in 23,250 gms. of hexane, was added to a flask. 83.5 gms. of awhite oil (mineral oil) was added in a first stage formed by an additionof 192 gms. of additional white oil while nitrogen blowing in order toevaporate hexane. The mixture was then heated to 60° C. and 0.7 gms. ofchlorine was added over 40 minutes at 60° -63° C. The mixture was thenstirred for 1/2 hour followed by stripping for an additional 11/2 hoursat a temperature of 60° -65° C. while maintaining a high nitrogensparging rate. Analysis showed that the polymer per se contained 0.95wt. % chlorine.

EXAMPLE 10

8000 gms. of a solution, previously formed by dissolving 1500 gms. ofPolymer E in enough hexane to make a 7.1 wt. % solution, was added to aflask. At room temperature, 25.2 gms. of bromine in 50 ml. of pentanewas added over 1 hour. The flask was heated to 40° C. for 1 hour and thered bromine color disappeared. The contents were sparged with nitrogenfor 30 minutes at 40° C. and then slowly overnight at room temperature.The hexane wax replaced with Solvent 100 Neutral oil by sparging withnitrogen and heating. The theoretical bromine content was 4.25 wt. %.

Synthesis of Halogenated Terpolymers EXAMPLES 11 to 16

Six terpolymers comprising ethylene, propylene and 5-chloromethylbicyclo(2,2,1)heptane-2 were synthesized with the aid of a Ziegler-Nattacatalyst combination comprising VOCl₃ -Et₃ Al₂ Cl₃ in an Al/V molarratio of 5 to 1. All runs were made at 35° C. for a residence time inthe reactor of 13.3 minutes, using a VOCl₃ + Et₃ Al₂ Cl₃ catalystconcentration of 0.010 pounds per 100 pounds of hexane solvent, and witha hydrogen feed of 20 ppm per part of ethylene feed by weight. Thereaction was carried out by continuously feeding the reactants, solvent,catalyst, etc., to the reactor and withdrawing a stream which containedthe polymer. The rate of feed of monomer, yields in pounds of polymerper pound of vanadium, and composition of the polymer product aresummarized in the following table.

                  Table I                                                         ______________________________________                                        Synthesis of Halogenated Terpolymers                                                                     Polymer                                            lbs Feed/                  Composition                                        Ex.  100 lbs Hexane   Yield    Wt.%  Wt.%                                     No.  C.sub.2.sup.=                                                                        C.sub.3.sup.=                                                                         ClMN(1) lbs/lb V                                                                             C.sub.2.sup.=                                                                       C1MN(2)                              ______________________________________                                        11   2.5    12.0    1.0     255    58.3  5.0                                  12   "      "       2.0     116    63.6  10.0                                 13   "      "       1.0     317    54.7  6.1                                  14   "      "       2.0     260    57.4  16.8                                 15   "      "       1.0     402    52.6  5.6                                  16   "      "       2.0     291    59.4  10.0                                 ______________________________________                                         C.sub.2.sup.= is ethylene.                                                    C.sub.3.sup.= is propylene.                                                   (1)C1MN is 5-chloromethyl norbornene-2.                                       (2)From chlorine analysis.                                               

While molecular weight was not determined, prior experience indicatedthat these terpolymers would have molecular weights in the range ofabout 30,000 to 70,000 M_(n).

Preparation of Sodium Pentaerythritol, i.e., The Alcoholate

In these examples, a commercial pentaerythritol was used which was about90% mono, about 8% di and about 1-2% tripentaerythritol.

EXAMPLE 17

100 ml. of dry dioxane was placed in a 250 ml. flask equipped with a barmagnet stirrer. 13.6 gms. of pentaerythritol was added, then 2.3 gms. ofsodium in small pieces. The flask was loosely stopped, to allow gas toescape, and was stirred overnight. The next day, the sodium haddissolved and reacted. The excess dioxane was then decanted and the wetsolid, i.e., the sodium pentaerythritol (Na-PE salt), used inexperiments later described.

EXAMPLE 18

11 gms. (0.2 moles) of sodium methoxide was added to 27 gms. (0.2 moles) of pentaerythritol in 100 ml. dioxane in a flask. The mixture wasstirred overnight. Solvent was slowly distilled off, while addingadditional dioxane, to maintain the dioxane level at about 100 ml. overan 8 hour period. By this method, substantially all of the methanolformed by the reaction was removed. The resulting material was a dioxaneslurry of the product, which was subsequently used as is.

EXAMPLE 19

11 gms. (0.48 moles) of sodium was reacted with 68 grams (0.495 moles)of pentaerythritol in 250 ml. of dimethyl formamide (DMF) under N₂ for20 hours. After the metal dissolved, the DMF was removed by high vacuumand a trap to yield a white powdery product.

EXAMPLE 20

555 gms. of pentaerythritol (4.05 moles) were put in a 5 liter flaskwith 4 liters of dry DMF. Under N₂ with stirring, 92 gms. of sodium (4moles) cut in pea sized pieces were added. All the sodium reacted in 48hours. One liter of benzene was added. The solid was filtered off underN₂ and washed with 1 gallon of benzene and then 1 gallon of pentane. Thepowdery white material, i.e., sodium pentaerythritol, was kept in a drybox till used.

Halo-Polymer - Metal Alcoholate Reaction Products

A typical reaction of halogenated polymer and the metal alcoholate iscarried out as follows:

EXAMPLE 21

About 2000 gms. of a solution containing 7 wt. % of halogenated PolymerA (containing 2.06% Cl) dissolved in Solvent 100 Neutral (minerallubricating oil of about 100 SUS viscosity at 100° F) is charged to afive liter four necked round bottom flask. The flask is put in anitrogen dry box and allowed to dry overnight. 27 gms. of sodium salt ofpentaerythritol of Example 20 is added in the dry box. The flask isremoved and set up with a N₂ sparge, thermometer, Teflon paddle stirrerand condenser. The flask is heated to 180° C. for 5 hours with strongstirring and nitrogen sparging. The resulting concentrate is faintlyhazy, but is cleared, by dilution with hexane, centrifuging in a tube at3000 RPM for 20 minutes, decanting the liquid, and evaporating off thehexane with a N₂ sparge on a steam bath. The final material is a clearyellow thick concentrate.

EXAMPLES 22 to 39

A series of hydroxylated polymers were formed in the general manner asdescribed in Example 21, but with variation in the reactants, conditionsof reaction, e.g., amounts, times, and temperatures, which variationsare summarized in Table II.

The resulting products of Examples 22 to 39 were tested for dispersancyability as follows:

A used automotive mineral lubricating oil, which had an originalviscosity of 325 SUS at 100° F., was obtained by pooling the oil drainedfrom the crankcases of a fleet of taxicabs operating in New York City.The used oil is centrifuged in heavy-walled 50 ml. tubes at 16,000 RPMfor one-half hour and the clear, supernatant oil decanted for use in thetest.

In conducting the test, 100 milligrams of the oil concentratescontaining 7 wt. % of the hydroxylated polymers to be tested are weighedinto 30 ml. beakers. Ten gms. of the centrifuged oil is added to eachbeaker and the samples heated on a steam bath with swirling until theadditive is completely dissolved and a homogeneous solution is obtained.The contents of each beaker are then transferred to pre-weighedcentrifuge tubes and the tubes stored in an oven at 280° F. (138° C.)for 16 hours. The tubes, including a number of blanks to which noadditive has been added but which have been heated to 280° F. for 16hours, are then centrifuged at 16,000 RPM for one-half hour and thesupernatant oil decanted and discarded. The tubes are then inverted in arack and allowed to drain for not more than fifteen minutes, after whichthe walls of each tube are rinsed with 25 ml. of pentane, taking carenot to disturb the sludge compacted in the tip of the tube. A second 25ml. portion of pentane is added to each tube and the sludge dispersedany any occluded oil dissolved by gentle shaking. The tubes are nowcentrifuged in an explosion-proof, refrigerated centrifuge at 16,000 RPMfor 1/2 hour, the pentane decanted and discarded. After rinsing theexterior of each tube with acetone, the tubes and contents are allowedto air-dry at room temperature and weighed. The weight of sludge isobtained by difference. The effectiveness of the additive is expressedas the wt. % sludge that is left in the tube as compared to the blank.Thus, 100% would indicate no dispersancy, with the lower percentagesindicating dispersancy.

The hydroxylated polymers, their preparation, and their effectiveness assludge dispersants are summarized in the following Table II:

                                      TABLE II                                    __________________________________________________________________________    PREPARATION OF HYDROXYLATED POLYMERS AND DISPERSANCY RESULTS                       Gm. of 7% S100N          Preparation                                          Solution of                                                                             Halo-Polymer   of Na-PE,                                                                            Time,                                                                             Temp.,                                                                            Hydroxyl                                                                           Dispersancy,                Example                                                                            Halo-Terpolymer                                                                         of Example                                                                            Gm. Na-PE                                                                            Example                                                                              Hours                                                                             °C.                                                                        No.  % of Blank                  __________________________________________________________________________    22   200       15      8**    17     20 145  --   60                          23   200       1*      32***  18     19 135  15.2 59                          24   250       4       1.20   19      3 150   8.9 61                          25   250       4       1.20   19      6 150  14.1 60                          26   250       4       1.20   19     22 150  15.1 58                          27   300       4       2.30   19      4 180   8.4 22                          28   300       4       2.30   19      6 180  --   36                          29   300       4       2.30   19      8 180  --   32                          30   300       4       2.30   19     10 180  2.84 24                          31   300       4       2.30   19     12 180  7.05 23                          32    40       5       0.1    19      1 25   --   --                          33   300       4       2.3    20      4 180  --   65                          34   300       4       2.3    20     10 180  --   64                          35   300       4       2.3    20     12 180  --   62                          36   300       3*      3.0    20      7 200  --   61                          37   300       3       3.0    20     53 150  --   56                                                 +(.5 gr.                                                                      DMF)                                                   38   300       3       3.0.   20     12 180  --   51                                                 +(0.1 gr.                                                                     MEOH)                                                  39   1800      8       72     20     . 5                                                                              180  --   23                                                 +(.1 gm.                                                                      MEOH)                                                  __________________________________________________________________________     *Different batches, but made in the manner of Examples 1 and 3,               respectively.                                                                 **8 grams of the wet solid of Example 17.                                     ***32 grams of the dioxane slurry of Example 18.                         

As seen by Table II, the oil soluble hydroxylated polymers of the Tablewere effective as sludge dispersants in a lube oil. Thus, Example 22reacted 200 grams of a lube oil solution containing 14 grams of thehalogenated polymer of Example 15 in 186 grams of the Solvent 100Neutral (S100N) lubricating oil with 8 grams of the wet sodium salt ofpentaerythritol (Na-PE) prepared according to Example 17, for 17 hoursat 145° C., which gave an oil solution of the hydroxylated polymer andprecipitated NaCl (which was separated out by centrifuging). Thehydroxylated polymer, when tested for Dispersancy, gave a reading of 60%of the blank, thereby indicating good dispersancy, (readings below 100%of blank indicate dispersancy, and the lower the % of blank, the greaterthe degree of dispersancy). As previously described, this dispersancytest centrifuges a used automotive crankcase oil to clear it of existingsludge, then heats in an oven at 280° F., samples of the cleared usedoil with the dispersant, so as to oxidize the oil in the presence of thedispersant, followed by centrifuging and washing to remove oil, to seehow much new sludge centrifuges out in the presence of the dispersant.The blank is a similar sample of the cleared oil, but withoutdispersant, which is also heated and then the new sludge that forms isalso separated by centrifugation. By comparing the weight of centrifugedsludge of the blank, with the weight of the centrifuged sludge of thedispersant-containing sample, the effectiveness of the dispersant inholding the sludge suspended in the oil is determined. In Example 22,the dispersant gave only 60% as much centrifugated sludge as the blank,which on the basis of prior experience with this test indicates a gooddispersant. The other Examples of Table II also indicate gooddispersants.

Examples 23 and 36 were made from halogenated polymers prepared in themanner of Examples 1 and 3 respectively, but were from different batchesof these halogenated polymers. In Example 23, 32 grams of the dioxaneslurry of the sodium pentaerythritol was used. Example 37 used 3 gramsof the sodium pentaerythritol of Example 20, along with 0.5 grams ofdimethyl formamide (DMF), which was added as a promoter to hasten thereaction on the idea that it would increase the polarity of the solvent.Example 38 used 3 grams of the sodium pentaerythritol of Example 20 with0.1 gram of methyl alcohol (MEOH) as a promoter, while Example 39 used72 grams of the sodium pentaerythritol with 0.1 gram of MEOH.

In some cases, the hydroxyl numbers of the resulting oil solution of thehydroxylated polymer were obtained. Thus, in Example 23, it had ahydroxyl number of 15.2 milligrams of KOH per gram of the oil solutioncontaining the hydroxylated polymer.

EXAMPLE 40

2000 grams of 7 wt. % solution of Polymer A chlorinated at 45° -50° C.to a 1.68 wt. % level in Solvent 100 Neutral oil was reacted with 16grams of the sodium salt of pentaerythritol (Example 20) for a total ofabout 5 hours at about 180° C. while sparging with nitrogen andvigorously stirring, following by dilution with hexane, centrifugationand evaporating the clear supernatent hexane solution on a steam bathwhile sparging with nitrogen. A clear yellow concentrate resulted. Thisconcentrate gave a dispersancy test of 29.4% of the blank in theaforedescribed dispersancy test.

A fully formulated 10W-30 SAE crankcase lubricating oil containingashless dispersant, antioxidants, and about 6.3 wt. % of a V.I. improverconcentrate containing about 7 wt. % of ethylene-propylene copolymer(which was not hydroxylated) as a viscosity index improver, was testedin a Sequence V-C engine test. For comparison, the same formulation wastested, but in place of the ethylene-propylene copolymer concentratethere was used about 6.2 wt. % of the concentrate of Example 40described above.

The Sequence V-C is definitively described in "Multicylinder TestSequences for Evaluating Automotive Engine Oils", ASTM Special TechnicalPublication 315F, 1973, page 133 ff. The V-C test evaluates the abilityof an oil to keep sludge in suspension and to keep varnish deposits fromthe pistons and other parts. The test results given below clearly showthe superior ability of a test oil incorporating a dispersant-viscosityindex improver of this invention.

                  TABLE III                                                       ______________________________________                                                   MS - V-C Test Results                                                                Piston        Total                                                    Sludge Skirt Varnish Varnish                                       ______________________________________                                        Oil with disper-                                                                           9.1      8.2           8.3                                        sant V.I. im-                                                                 prover of                                                                     Example 40                                                                   Oil with ethylene-                                                                         8.0      8.2           7.6                                        propylene V.I.                                                                improver                                                                     Passing criteria                                                                           8.5      8.0           8.0                                        for test                                                                     ______________________________________                                    

In the above test, the ratings are on a scale of 0 to 10, where 0 isextremely poor, and 10 is completely clean. As seen by the above data inTable III, the use of hydroxylated V.I. improving polymers of theinvention, in place of a non-hydroxylated polymer, significantlyimproved the performance of the oil composition in keeping the engineclean.

What is claimed is:
 1. An oil soluble hydroxylated polymer having sludgedispersing properties in crankcase motor oil, having a molecular weightof 1000 to 500,000 M_(n), and containing about 0.1 to about 15 wt. %oxygen, wherein said hydroxylated polymer is the reaction product of ahalogen containing polymer having 0.1 to 7.0 wt. % halogen and a metalsalt of a polyol, wherein said halogen containing polymer is selectedfrom the group consisting of:a. halogenated copolymer of ethylene and aC₃ to C₁₈ straight or branched chain-olefin; b. halogenated terpolymercomprising ethylene, a C₃ to C₁₈ straight or branched chain-olefin and aC₅ to C₁₄ acyclic or alicyclic non-conjugated diolefin; and c.halogenated terpolymer comprising ethylene, a C₃ to C₁₈ straight orbranched chain-olefin and a C₅ to C₁₄ acyclic or alicyclic halo-olefincontaining 1 to 2 halogens, wherein said polymers (a), (b) and (c) eachcomprise in the range of about 30 to 85 mole % ethylene, about 15 to 70mole % of said C₃ to C₁₈ alpha olefin, and up to about 20 mole % of saiddiolefin or said halo-olefin in the case of said terpolymers, andwherein said polyol is selected from the group represented by theformulae: ##STR6## wherein R is selected from the group consisting ofhydrogen, C₁ to C₂₀ straight or branched chain alkyl radicals, methylol,hydroxy alkyl, pentaerythritol, amine, chlorine, nitro, or nitriloradicals; R' is a C₂ to C₂₀ straight, branched or alicyclic chain,alkylene radial; R" is a C₂ to C₄ alkylene radical; and x and y can varyfrom 1 to
 50. 2. A hydroxylated polymer according to claim 1, whereinsaid hydroxylated copolymer has a molecular weight of about 20,000 to100,000, an oxygen content of 0.2 to 10.0 wt. %, and wherein said alphaolefin is a C₃ to C₈ olefin.
 3. A hydroxylated terpolymer according toclaim 1, wherein said polymer is a hydroxylated terpolymer of ethylene,propylene and said diolefin.
 4. A hydroxylated terpolymer according toclaim 3, wherein said diolefin is selected from the group consisting of5-ethylidene norbornene-2, and 1,4-hexadiene.
 5. A hydroxylated polymeraccording to claim 1, wherein said polyol is pentaerythritol.
 6. Ahydroxylated polymer according to claim 5, wherein said polymer is ahydroxylated terpolymer of ethylene, propylene, and said diolefin.